Water soluble phthalocyanine dyes



v 3,320,275 Unlted States Patent Ofihce may M dyestuffs which possess excellent substantivity for cellulosic fibers and which produce dyeings on cellulosic fibers WATER SOLUBLE PHTHALOCYANINE DYES l1i K. Dien and Walter B. Richards, Erie County, N.Y., assignors to Allied Chemical Corporation, New York,

characterized by excellent fastness to light and washing. These new dyes are obtained by heating a halogenomethyl N.Y-, a corporation of New York 5 phthalocyanine compound with a polysubstituted hydra- No Drawing. Filed July 29, 1963, Ser. No. 298,441 zine compound, the latter preferably in excess over the 3 Claims. (Cl. 260-4145) stoichiometric amount, in an organic solvent which does not react with either component under the conditions of This invention relates to novel Water Soluble dyes and the reaction. The reaction is elfected at a temperature to processes for their manufacture and use. More parf at least and preferably at to C l, it relates to novel dyestuffs Prepared y the The products of this invention are essentially hydraaction of halogeuomethyl derivatives of water insoluble Zonium salts, as represented by general Formula I below ilhthalocyahihes with Substituted hydrazihes- It is theoretically possible, and indeed highly probable, in

It is known to P p quaternary and ternary Salt some instances, for the reaction to proceed along a diflerdyestufi dtifivaties of Water insoluble P y y y 60111- cut course and result in the formation of, as by-product, Pounds y heating a halogeflomfilhyl derivative of the a substituted hydrazine, II, and/or salt III thereof. The polycyclic aryl compound (1) with a tertiary amine to reactions may be represented by the following equations:

I Poy OH2N-X R'*-NR3 n r r R4 R1 PcywHgXWrn H rmom-z r-r'msfinmx III Pcy(GH -NN -R X)n it R2 (R Hydrogen) form a quaternary ammonium salt, (2) with a mercapto wherein n is at least 1, X is a halogen of the group chlorine derivative and subsequently treating the so-obtained suland bromine, R and R are the same or different memphide with an ester known to convert sulphides into ternary bers of the group consisting of alkyl (e.g. methyl, ethyl, sulphonium salts, or (3) with a thiourea containing at propyl, amyl, octyl, dodecyl) cyclohexyl, aralkyl (e.g. least one reactive hydrogen to form an isothiouronium benzyl, p-nitrobenzyl, m-methoxybenzyl, o-chlorobenyl),

salt. These known derivatives are more water soluble aryl (phenyl, 2,4-dinitrophenyl, S-trifiuoro-methylphenyl), than the polycyclic aryl compounds from which they are R being other than aryl when R is aryl, and R and R derived and as such possess greatly improved substanare the same or difierent members of the group consisttivity for cellulosic materials, e.g., cotton, paper and the 40 ing of hydrogen and radicals represented by R and Pcy like. In use, under mill conditions, these dyestufis are represents a phthalocyanine group. somewhat lacking in water solubility and require the While the novel dyestuifs of this invention are essensolubilizing assistance of surface active agents. The apfi l y hydrazonium C mpounds, they may contain minor amounts of the above mentioned by-products.

plication of dyestuffs of this known class has been ac- The novel products of our invention can be applied to complished by a rather complicated process involving steaming, chromate fixing, and soaping steps which proccellulosic fibers in the manner of conventional direct dyeess offers little if any advantages over the vatting pro- Stuffs and the dyel'hgs 80 Obtained are fast to light and cedure normally used for the application of many of the t0 g- The new y are Particularly useful as polycyclic aryl compounds from which these more soluble colorants for P p both Sized and uhsiled, the dyeings derivatives are derived. Further, the suggested applicabeing further Charactelized y Substantial freedom from tion method, besides being somewhat arduous, involves d dH SS. considerable expense for specialized equipment. The more Suitable halogenomethyl derivatives of polycyclic aryl recent literature in this field contains numerous sugcompounds for use ill this invent-i011 include p y gestions of variations of the general preparative pronines, both 'Ihfilal free and metal Containing, and their cedure, but so f as We are aware none f h newer derivatives. Representative members of this group of suitderivatives have been entirely successful in overcoming able intermediate chmpohhds include the polyhalomfithyl the basic difiiculties of this class of dyestuffs. derivatives of It is, therefore, a principal object of this invention to metal free phthalocyanine devise new and improved water soluble dyes. copper phthalocyanine A more specific object is to devise novel water-soluble cobalt phthalocyanine dyes which are reaction products of halogenomethyl-connickel phthalocyanine taining phthalocyanines and polyalkylhydrazines and which zinc phthalocyanine are easily applicable to cellulosic materials by direct dyeiron phthalocyanine ing methods. magnesium phthalocyanine Another1 object is to provide a method of synthesis of aluminum phthalocyanine these: Hove Water h yes. as well as the polyhalogenated e. tetrachloro co er Still another ob ect is to provide a method of dyemg h h l i palyphenyl f tetraphenyl zi 06111110510 mflteflflls uslhg the hovel y phthalocyanine), poly sulfamyl (e.g., tetra sulfamyl zinc O h obiects e obvwus m the l w s d phthalocyanine) and the like derivatives of this well- SCYIPUOH Of IYIVBHUOII- known class of organic pigments. The halogenomethyl We have now discovered a new class of water soluble groups which can be chloromethyl or brornomethyl groups are attached to aromatic ring carbons of the phthalocyanine radical. At least one and as many as eight halogenomethyl groups can be present although phthalocyanines containing from two to five such groups are preferred. Such derivatives which contain at least one and preferably from two to five halogenomethyl moieties per phthalocyanine molecule are desirable starting materials for reaction With polyalkylhydrazines.

The halogenomethyl derivatives can be made by several known procedures. For example, the chloromethyl copper phthalocyanine is conveniently prepared by the action of paraformaldehyde on copper phthalocyanine in a mixture of chlorosulfonic and sulfuric acids at temperatures within the range of 85 to 95 C.

Suitable hydrazines for use in our new process possess at least one nitrogen having two substituents other than hydrogen and may have all hydrogens replaced by alkyl, aryl, or aralkyl substituents. Specific representative examples of such hydrazines include:

1,1-dimethylhydrazine 1,1-diethylhydrazine l-benzyll -methylhydrazine l-benzyl- 1- m-bromophenyl) hydrazine l-benzyl-l ,2-dimethylhydrazine l-benzyl-l (p-methoxyphenyl) hydrazine 1-(4-biphenyl) -1-methylhydrazine 1,1 -bis( o-bromobenzyl) hydrazine 1- (2-butoxyphenyl) -1-ethylhydrazine l-butyl- 1 -phenylhydrazine 1,1-dibenzylhydrazine 1,2-dibenzyl-1,Z-dimethylhydrazine 1,1-dibutylhydrazine 1,1-dicyclohexylhydrazine 1,1-diethyl-Z-phenylhydrazine 1,1-dipentylhydrazine 1,2-dimethyll-dodecylhydrazine 1 l-naphthyl) -1-methylhydrazine 1,1 ,2,-tribenzylhydrazine 1,1 ,Z-trimethylhydrazine Toluene is a convenient solvent for use in producing the novel compounds of this invention since it boils, in the presence of the reactants, at a temperature below 110 C. and the reactants are sufficiently soluble and the product is quite insoluble therein. Other suitable solvents which can be used include benzene and xylene.

The reaction is continued for a sufiicient period to obtain a substantially complete reaction, i.e., about to 24 hours, after which the product can be separated in any convenient manner as by filtration, evaporation and crystallization, etc. The product is usually obtained in a form sufficiently pure to be used without further purification.

The invention will be illustrated by the following examples. Inasmuch as variations in the details set out in these examples will be obvious to those skilled in this art and such variations can be made without departing from the scope or spirit of our invention, it will be understood that the examples are for illustrative rather than limiting purposes. Parts are by weight and temperatures are given in degrees centigrade.

EXAMPLE I To about 150 parts of dry toluene, parts tris(chloromethyl) copper phthalocyanine (13.8% Cl) and 7.5 parts of 1,1-dimethylhydrazine are charged. The mixture is heated to boiling under reflux conditions and maintained thereat (T=about 104) for 18 /2 hours. The slurry is cooled to about 25 and filtered. The filter cake is washed with about 75 parts of toluene and then with about 120 parts of ethyl alcohol. The washed cake is dried in air. The resultant bright blue powder weighs 18.0 parts and is quite soluble in water. It dyes cotton from a neutral aqueous bath in bright blue shades which possess excellent fastness to washing. Unsized paper is dyed a strong, bright blue shade of excellent fastness to light and freedom from two sidedness.

EXAMPLE II A mixture of 50 parts of 100% sulfuric acid and 300 parts of chlorosulfonic acid is cooled to below 30 and then 30 parts of zinc phthalocyanine are added. The mixture is agitated for about /z-hour and while maintaining the temperature below 30, 100 parts of paraforrnaldehyde are added. The mixture is agitated at about 25 for /2-hour while excluding atmospheric moisture, and then it is heated, over about two hours, to and maintained at 94 to 96 for 6 /2 hours. The mass is cooled to about 25 and then drowned in 2000 parts of ice and water. The aqueous mass is diluted to about 4000 parts water metric volume with cold water and the resultant slurry is filtered. The filter cake is washed well with cold water and then with ethyl alcohol. The wash cake is dried at 65 to The product is a blue green solid, weighing 48.5 parts and containing 16.7% chlorine. Inasmuch as tris (chloromethyl) zinc phthalocyanine contains 14.95% Cl while the tetrakis chloromethyl derivative contains 18.40% Cl, the product prepared herein is apparently a mixture of the two.

A mixture of 15 parts of the above prepared tris/ tetrakis (chloromethyl) zinc phthalocyanine and 8.6 parts of 1,1-dimethylhydrazine in 150 parts of dry toluene is heated to boiling and refluxed at about 102 for about 17 hours. The mixture is cooled to about 25, diluted with about parts of acetone and the slurry is filtered. The filter cake is washed with aqueous acetone until the wash liquor is practically colorless. The washed cake is dried in air. The resultant product dyes paper, both sized and unsized, directly in strong yellow-green shades of excellent fastness to light.

EXAMPLE IV A solution of one part of the product of Example I above in parts of boiling water is diluted with 250 parts of distilled water and 50 parts of 20% aqueous solution of sodium chloride. A 20 part skein of cotton yarn is entered into the dyebath which is gradually raised to the boil and maintained thereat for one hour while intermittently working the skein in the dyebath. Thereafter, the dyed skein is removed from the dyebath, rinsed thoroughly in warm Water then in cold Water and dried. The resultant skein is dyed a deep greenish blue shade of excellent levelness and freedom from speckiness.

From the foregoing description of our invention and the detailed examples illustrating several specific practical manifestations thereof, it will be apparent that a new class of water soluble direct dyes for cellulosic fibers characterized by excellent fastness properties has been devised.

It will be appreciated that the foregoing examples are illustrative and that many variations in the specific details set out therein can be employed without departing from the spirit of the invention.

We claim:

1. A novel water soluble compound having substan- 5 6 tivity for cellulosic materials and having the general forcyanine group or metal free or metal containing polymula chloro, tetraphenyl, or tetrasulfamyl phthalocyanine Rt p;

and wherein the methylene group is attached to an aryl Fey CHFNTX 5 nucleus of the phthalocyanine group.

R2 2. The compound of claim 1 wherein n is 2 to 5 and Rs R and R are lower alkyl. L 3. The compound of claim 2 wherein R and R are methyl, R and R are hydrogen and X is chlorine.

wherein It stands for an integer l to 8; Referemes CW by the Examine! X is Chlorine bromine; UNITED STATES PATENTS R and R are the same or different radlcals of the group 2,542,327 2/1951 Haddock et aL IMG 3145 consisting of alkyl containing 1 to 12 carbon atoms, 3 057 873 /1962 Pugin fit a1. 26O 314 5 cyclohexyl, benzyl, nitrobenzyl, methoxy benzyl and 3 063 780 11/1962 Roach et a1 8 1 chlorobmyl phenyl z4'dinitrophenyl and 3 143 574 8/1964 Brown id( )608 methylphenyl, provided that when R is aryl R is alkyl 5 1 6/1965 g -gg-a- 26O 146 or aralkyl;

R and R are the same or dilferent members of the group WALTER MQDANCE, Primary Examiner consisting of hydrogen and radicals represented by R Pcy represents a metal free or metal containing phthalo- JAMES PATTEN Assistant Examine"- 

1. A NOVEL WATER SOLUBLE COMPOUND HAVING SUBSTANTIVITY FOR CELLULOSIC MATERIALS AND HAVING THE GENERAL FORMULA 